CN109235024A - A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load - Google Patents

A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load Download PDF

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CN109235024A
CN109235024A CN201811025824.9A CN201811025824A CN109235024A CN 109235024 A CN109235024 A CN 109235024A CN 201811025824 A CN201811025824 A CN 201811025824A CN 109235024 A CN109235024 A CN 109235024A
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mos
nis
carbon cloth
heterogeneous
nano
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CN109235024B (en
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符秀丽
官顺东
彭志坚
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Beijing University of Posts and Telecommunications
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Beijing University of Posts and Telecommunications
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/53—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with hydrogen sulfide or its salts; with polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to a kind of NiS-MoS of carbon cloth load2Heterogeneous nano-chip arrays structure and preparation method thereof, belongs to technical field of nanometer material preparation.Composite material proposed by the present invention is that have multistage three-dimensional box rack and panel construction, NiS-MoS at array-like in conductive three-dimensional carbon cloth carrier surface homoepitaxial2Heterogeneous nanometer chip architecture, wherein MoS2It is coated on the surface of NiS.In a kettle, respectively using nickel acetate, ammonium molybdate and thiocarbamide as nickel source, molybdenum source and sulphur source, lauryl sodium sulfate is surfactant to the present invention, and by one step hydro thermal method, growth obtains NiS-MoS directly on carbon cloth2Heterogeneous nano-chip arrays structure.This method is with condition is controllable, apparatus and process is simple, yield is big, at low cost and advantages of environment protection.Hetero nano structure product purity obtained is high, and pattern and composition are controllable.This nano structural material (is with a wide range of applications in electrochemical catalysis (hydrogen manufacturing, oxygen processed), energy storage in terms of supercapacitor, lithium ion battery.

Description

A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and its system of carbon cloth load Preparation Method
Technical field
The present invention relates to a kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load, Belong to technical field of nanometer material preparation.
Background technique
Molybdenum sulfide (MoS2) it is used as typical stratiform two dimension transition metal semiconductor material, there is class graphene-structured, Unique physicochemical properties make its photoelectronics, photoelectrocatalysis, in terms of have a wide range of applications. However, one pack system MoS2Material is difficult to play its excellent properties completely.For example, MoS2Catalyzing manufacturing of hydrogen reaction high activity site It is distributed across on the Mo atom of its lamellar structure edge exposure, the activity in these sites close to your best gold generally acknowledged at present Belong to Pt catalyst, and its main planar portion for occupying larger area is then active lower, and poorly conductive, this leads to pure MoS2Reality It is unsatisfactory that border is catalyzed H2-producing capacity.For another example, MoS2Two-dimensional layered structure there is biggish specific surface area, while its interlayer is It is connected by weaker Van der Waals force, this facilitates ion, molecule is migrated in its interlayer, is ideal energy storage material, has excellent Different capacitive property and storage lithium, storage sodium performance, can be used for supercapacitor and lithium ion, sodium-ion battery etc..However, pure MoS2 It is easy to shrink in charge and discharge process to reunite, its pattern is caused to be destroyed, performance decline；Simultaneously because its poorly conductive, no Conducive to the transmission of electronics, it is poor to eventually lead to its high rate performance.Therefore, by MoS2With the compound building nanometer of other semiconductor materials Heterojunction structure is research hotspot (U.Gupta&C.N.R.Rao, the Hydrogen effectively solved these problems at present generation by water splitting using MoS2and other transition metal dichalcogenides.Nano Energy,2017,41:49-65)。
In numerous MoS2In hetero nano structure composite material, MoS2It is especially concerned by people with the heterojunction structure of nickel sulfide.Sulphur Change nickel (NiS, Ni3S2、NiS2、Ni3S4Deng) belong to narrow band gap transition metal semiconductor, there is excellent electric conductivity, and reserves are rich Richness, cheap, preparation easy to process.Meanwhile nickel sulfide also has preferable electro-catalysis hydrogen manufacturing and oxygen activity processed, and abundant Redox active site, also have extensive utilization in terms of electrochemical catalysis and energy storage.It is reported that Ni3S4-MoS2It is heterogeneous Nano particle (J.Zhang, et al., Interface engineering of MoS2/Ni3S2heterostructures for highly enhanced electrochemical overall-water-splitting Activity.Angewandte Chemie International Edition, 2016,55 (23): 6702-6707) and Ni3S2-MoS2Heterogeneous nanometer rods (Y.Q., Yang, et al., Heteronanorods of MoS2-Ni3S2as efficient and stable bi-functional electrocatalysts for overall water splitting.ACS Catalysis, 2017,7:2357-2366) the nano-heterogeneous structures composite material such as, decomposes water and super electricity in electrochemical catalysis Excellent performance is shown in terms of container.
However, compared to the MoS of other patterns2With nanometer nickel sulfide heterojunction structure, two-dimensional sheet heterojunction structure has very More advantages are more advantageous to and play MoS2With the respective performance characteristics of nickel sulfide.For example, two-dimensional sheet structure has compared with Large ratio surface Product, this is conducive to the shuttle and diffusion of reactive material therebetween, can be from the progress for kinetically accelerating electrochemical reaction；Meanwhile Sheet Heterogeneous Composite can effectively expose MoS2Edge active site, and make MoS2Original lamellar structure can obtain Intact holding effectively plays its every excellent characteristics.But there is presently no about NiS-MoS2The report of heterogeneous nanometer sheet Road.
In addition to this, select suitable collector as carrier, directly using this carrier as substrate grown array-like Nanometer sheet can farthest utilize the design feature of two-dimension nano materials to construct three-dimensional box rack and panel construction.Together When, multistage frame structure can effectively avoid active material (such as MoS in electrochemical catalysis reaction process2With nickel sulfide) Reunite, the structure and pattern of sheet-like array is helped to maintain, to improve the stability of catalyst.Currently, using more Current collector material be metal material, such as nickel foam, foam copper, stainless (steel) wire and titanium metal plate, they have certain Chemical activity is conducive to directly grow inorganic active material on its surface.However, utilization is highly conductive relative to metal material Property carbon material (such as carbon fiber, carbon cloth, carbon paper) there is lot of advantages as collector, such as they are light-weight, chemically Can stablize, is environmental-friendly etc., be more suitable for it is various assemble, flexible electrochemical device.But it is also good just because of carbon material Good chemical inertness is difficult directly so that the compatibility between carbon material and various inorganic material is poor effectively on its surface Growth activity substance.
Currently, the method for preparing heterogeneous nano material is mainly two-step synthesis method, including two step chemical vapor depositions and two One-step hydrothermal, they can the pattern to heterogeneous nano material effectively controlled.However, this mode successively grown is not Conducive to close contact between various active substance and compound, it is difficult to obtain more effective active interface, lead to composite wood The performance of material is undesirable.Therefore, more and more work directly synthesize hetero nano structure, the difficulty of this method in exploration one-step method Point is to control the pattern and structure of composite material.Meanwhile inorganic active material is grown in inert carbon substrate and often need Substrate is pre-processed, such as carry out surface oxidation etching, the experimental procedure of these methods using the concentrated sulfuric acid, concentrated nitric acid etc. It is cumbersome and have certain risk, be unfavorable for actual production application.Therefore, develop a kind of simple effective method make it is inorganic Active material is grown directly upon in carbon substrate and is of great significance.
For the present invention using nickel acetate, ammonium molybdate, thiocarbamide as nickel source, molybdenum source and sulphur source, lauryl sodium sulfate is living for surface Property agent, ingenious have the characteristics that hydrophilic-hydrophobic pair property groups using lauryl sodium sulfate, by simple one step hydro thermal method, Directly NiS-MoS has been grown on three-dimensional carbon cloth2Heterogeneous nano-chip arrays structure.This method controllable, equipment with condition Simple process, yield is big, at low cost and advantages of environment protection, easily accomplishes scale production.Heterogeneous nanometer sheet battle array obtained Array structure product purity is high, and pattern and composition are controllable.This composite material constructs a kind of three-dimensional box rack and panel construction of multistage, with Carbon fiber is as conducting matrix grain, in the NiS-MoS of its surface uniform load array-like2Heterogeneous nanometer sheet, wherein MoS2Uniformly cladding In the surface of NiS nanometer sheet, a large amount of heterogeneous interface is formd.Due to its unique pattern, structure and compositing characteristic, this carbon The NiS-MoS of cloth load2Heterogeneous nano-chip arrays structure is in electrochemical catalysis hydrogen production by water decomposition and oxygen processed, electric chemical super capacitor Device and lithium ion battery etc. are with a wide range of applications.
Summary of the invention
It is an object of the present invention to propose a kind of NiS-MoS of carbon cloth load2Heterogeneous nano-chip arrays structure.It is this Composite material is by the NiS-MoS of the array-like of three-dimensional carbon cloth and its surface uniform load2Heterogeneous nanometer sheet is constituted.This A kind of three-dimensional box rack and panel construction of multistage is built in kind composite material, it is uniform on its surface using carbon fiber as conducting matrix grain Load the NiS-MoS of array-like2Heterogeneous nanometer sheet.Wherein, MoS2It is uniformly wrapped on the surface of NiS nanometer sheet, is formd a large amount of Heterogeneous interface can be conducive to the shuttle and diffusion of electrochemical reaction substance, from kinetically promoting electrochemical reaction speed；Together When, biggish specific surface area helps sufficiently to expose NiS and MoS2Active site, improve reactivity；In addition, its frame Formula structure can also effectively avoid NiS and MoS2Reunion, the structure and pattern of nano-chip arrays are helped to maintain, to improve this The stability of kind composite material.Therefore, the NiS-MoS of this carbon cloth load2Heterogeneous nano-chip arrays structure is in electrochemistry Before catalytic decomposition water hydrogen manufacturing and oxygen processed, electric chemical super capacitor and lithium ion battery etc. etc. have a wide range of applications Scape.
The second object of the present invention is to provide the NiS-MoS of this carbon cloth load2Heterogeneous nano-chip arrays structure is corresponding Preparation method.This method can make NiS-MoS2Heterogeneous nanometer sheet at array-like, uniformly, be closely coated on carbon fiber On, and Product yields are big, purity is high, composition and morphology controllable；This method has equipment and simple process, synthesis growth simultaneously The advantages that condition is stringent controllable, product yield is high, low in cost, production process clean and environmental protection.
In order to reach above-mentioned target, the NiS-MoS of carbon cloth load proposed by the present invention2Heterogeneous nano-chip arrays structure, It is characterized in that, the product is by the NiS-MoS of the array-like of three-dimensional carbon cloth and its surface uniform load2Heterogeneous nanometer Piece is constituted, and wherein carbon fiber diameter is 8-12 μm, and carbon cloth is with a thickness of 0.25-0.35mm, nanometer sheet thickness about 20-50nm, diameter Between 300-600nm；A kind of three-dimensional box rack and panel construction of multistage is built in the product, using carbon fiber as conductive bone Frame, in the NiS-MoS of its surface uniform load array-like2Heterogeneous nanometer sheet, wherein MoS2It is uniformly wrapped on the surface NiS.
The NiS-MoS of carbon cloth load provided by the invention2The preparation method of heterogeneous nano-chip arrays structure, feature exist In using nickel acetate, ammonium molybdate, thiocarbamide as nickel source, molybdenum source and sulphur source, lauryl sodium sulfate is surfactant, passes through one One-step hydrothermal, directly carbon cloth surfaces uniformly, closely grow NiS-MoS2Heterogeneous nano-chip arrays structure.
The NiS-MoS of carbon cloth load proposed by the present invention2The preparation method of heterogeneous nano-chip arrays structure, including following step Rapid and content:
(1) carbon cloth is successively cleaned by ultrasonic with acetone, 1-2mol/L aqueous hydrochloric acid solution and deionized water respectively in advance 0.5-1 hours, and dried at 60 DEG C, it saves backup；
(2) the pure nickel acetate of commercially available analysis, ammonium molybdate, thiocarbamide and lauryl sodium sulfate powder are put into beaker, then plus Entering deionized water and being sufficiently stirred mixes it uniformly；Recycle sodium hydrate aqueous solution adjust reactant mixed solution pH value to Between 5.8-7.0.
(3) reactant mixed solution is transferred in autoclave, is put into clean carbon cloth, seal reaction kettle.
(4) reaction kettle is moved in electric furnace, and is heated to 160-200 DEG C and keeps the temperature 8-12 hours；Then it naturally cools to Room temperature.
(5) after opening reaction kettle, carbon cloth is taken out from reaction kettle, and alternately rinsed 3-5 times with deionized water and alcohol；So It dries afterwards at 60 DEG C to get the NiS-MoS loaded to the carbon cloth2Heterogeneous nano-chip arrays.
(6) at room temperature, it is saved backup in drying box.
In the above preparation method, carbon cloth described in the step (1) is water-soluble with acetone, 1-2mol/L hydrochloric acid respectively in advance Liquid and deionized water are successively cleaned by ultrasonic 0.5-1 hours.
In the above preparation method, the carbon cloth cleaned in the step (1) is dried at 60 DEG C in an oven.
In the above preparation method, nickel acetate, ammonium molybdate, thiocarbamide and lauryl sodium sulfate are in the step (2) The commercially available pure powder reagent of analysis.
In the above preparation method, acetic acid nickel concentration is 0.03- in control reactant mixed solution in the step (2) 0.05mol/L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, dodecyl Sodium sulfate concentration is 0.15-0.25mol/L.
In the above preparation method, it is water-soluble that sodium hydroxide used in reactant mixed solution pH value is adjusted in the step (2) Liquid concentration is 0.5-1.0mol/L, and reactant mixed solution pH value is 5.8-7.0 after adjusting.
In the above preparation method, the loading of reactant mixed solution is in step (3) the mesohigh reaction kettle 50%-80%.
In the above preparation method, in the step (3) depending on the size visual response kettle size of carbon cloth, and it is vertically soaked Enter in reactant mixed solution.
In the above preparation method, heating schedule is reacted in the step (4) are as follows: be heated to the rate of 5-20 DEG C/min 160-200 DEG C and 8-12 hours are kept the temperature, then naturally cools to room temperature.
In the above preparation method, carbon cloth sample deionized water and alcohol alternately rinsing 3-5 times in the step (5).
In the above preparation method, drying carries out at 60 DEG C in an oven in the step (5).
In the above preparation method, final sample saves in drying at room temperature case in the step (6).
Present invention is characterized in that in the NiS-MoS for preparing the carbon cloth load2The process of heterogeneous nano-chip arrays structure In, it is ingenious to have using lauryl sodium sulfate in the solution containing the source Ni, Mo, S using three-dimensional carbon cloth as carrier There is the characteristics of hydrophilic-hydrophobic pair property group, by simple one step hydro thermal method, NiS-MoS has directly been grown on carbon cloth2It is different Matter nano-chip arrays structure.During the reaction, the hydrophilic radical in lauryl sodium sulfate and Mo, Ni group phase in solution In conjunction with, and hydrophobic grouping is then easy in conjunction with inert carbon surface, therefore the NiS and MoS generated in reaction2It can be uniformly and firm Admittedly carbon fiber surface forming core grow.In addition, lauryl sodium sulfate is divided in water during subsequent growth after forming core Solution forms water-oil two-phase mixtures system, which helps to grow sheet nanostructure；NiS and MoS simultaneously2Between With symplastic growth effect, finally on carbon cloth growth obtain it is with multistage three-dimensional box rack and panel construction, at array-like NiS-MoS2Heterogeneous nanometer chip architecture.
The present invention has the advantages that preparing the NiS-MoS of the carbon cloth load using this technology2Heterogeneous nano-chip arrays knot Structure, equipment and simple process, synthesis growth conditions is stringent controllably, product yield is high, low in cost, production process clean and environmental protection； NiS-MoS obtained2Heterogeneous nano-chip arrays structure yield is big, with high purity, composition and pattern uniform, controllable；Wherein NiS- MoS2Heterogeneous nanometer sheet is coated on carbon fiber at array-like, uniformly, closely, and MoS2It is uniformly wrapped on the surface of NiS, shape At a large amount of heterogeneous interface.
Detailed description of the invention
Fig. 1 is the NiS-MoS of the load of carbon cloth obtained by the embodiment of the present invention 12The X- of heterogeneous nano-chip arrays structure is penetrated Line diffraction pattern and its parsing result
Fig. 2 is the NiS-MoS of the load of carbon cloth obtained by the embodiment of the present invention 12The low power of heterogeneous nano-chip arrays structure Stereoscan photograph
Fig. 3 is the NiS-MoS of the load of carbon cloth obtained by the embodiment of the present invention 12The high power of heterogeneous nano-chip arrays structure Stereoscan photograph
Fig. 4 is the NiS-MoS of the load of carbon cloth obtained by the embodiment of the present invention 12NiS- in heterogeneous nano-chip arrays structure MoS2The transmission electron microscope photo of heterogeneous nano-chip arrays
Specific embodiment
Below with reference to embodiment, technical scheme is described further.
The NiS-MoS of carbon cloth load proposed by the present invention2Heterogeneous nano-chip arrays structure, which is characterized in that the product It is by the NiS-MoS of the array-like of three-dimensional carbon cloth and its surface uniform load2Heterogeneous nanometer sheet is constituted, wherein carbon fiber Diameter is 8-12 μm, and carbon cloth is with a thickness of 0.25-0.35mm, and nanometer sheet thickness about 20-50nm, diameter is between 300-600nm；Institute The three-dimensional box rack and panel construction that a kind of multistage is built in product is stated, using carbon fiber as conducting matrix grain, in its surface uniform load The NiS-MoS of array-like2Heterogeneous nanometer sheet, wherein MoS2It is uniformly wrapped on the surface NiS.
The NiS-MoS of carbon cloth load provided by the invention2The preparation method of heterogeneous nano-chip arrays structure, feature exist In using nickel acetate, ammonium molybdate, thiocarbamide as nickel source, molybdenum source and sulphur source, lauryl sodium sulfate is surfactant, passes through one One-step hydrothermal, directly carbon cloth surfaces uniformly, closely grow NiS-MoS2Heterogeneous nano-chip arrays structure.
The NiS-MoS of carbon cloth load proposed by the present invention2The preparation method of heterogeneous nano-chip arrays structure, successively include with Lower step and content:
(1) carbon cloth is successively cleaned by ultrasonic with acetone, 1-2mol/L aqueous hydrochloric acid solution and deionized water respectively in advance 0.5-1 hours, and dried at 60 DEG C, it saves backup.
(2) the pure nickel acetate of commercially available analysis, ammonium molybdate, thiocarbamide and lauryl sodium sulfate powder are put into beaker, then plus Entering deionized water and being sufficiently stirred mixes it uniformly, and controlling acetic acid nickel concentration in reactant mixed solution is 0.03-0.05mol/ L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, and lauryl sodium sulfate is dense Degree is 0.15-0.25mol/L.The sodium hydrate aqueous solution of 0.5-1.0mol/L is recycled to adjust the pH value of reactant mixed solution To between 5.8-7.0.
(3) after the reactant mixed solution for filling 50%-80% in a high pressure reaction kettle, it is dipped vertically into clean carbon cloth, Seal reaction kettle.
(4) reaction kettle is moved in electric furnace, and the rate of 5-20 DEG C/min is heated to 160-200 DEG C and to keep the temperature 8-12 small When；Then room temperature is naturally cooled to.
(5) after opening reaction kettle, carbon cloth is taken out from reaction kettle, and alternately rinsed 3-5 times with deionized water and alcohol；So It dries afterwards at 60 DEG C to get the NiS-MoS loaded to the carbon cloth2Heterogeneous nano-chip arrays structure.
(6) at room temperature, it is saved backup in drying box.
The NiS-MoS of obtained carbon cloth load2Heterogeneous nano-chip arrays structure sample, visually appear to be ater and A shaggy piece of cloth.Under scanning and transmission electron microscopy, it may be observed that a large amount of criss-cross nanometer sheets, equably Perpendicular to carbon fiber surface, at array-like.X-ray diffraction analysis shows, this material be high-purity 2H phase MoS2With six sides The compound of phase NiS.
In short, with this technology high-purity, highdensity array-like NiS-MoS can be grown in carbon fiber surface high yield2It is different Matter nanometer chip architecture.
Embodiment 1: the carbon cloth of one piece of 2.5 × 4cm size with acetone, 1mol/L aqueous hydrochloric acid solution and is gone respectively in advance Ionized water is successively cleaned by ultrasonic 0.5 hour, and dries at 60 DEG C, saves backup.
In 100mL beaker, 0.224g nickel acetate, 0.074g ammonium molybdate, 0.137g thiocarbamide and 1.73g dodecyl is added Then 30mL deionized water is added in sodium sulphate, be stirred well to solution clarification；0.5mol/L sodium hydrate aqueous solution is slowly added dropwise The pH value of reactant mixed solution is adjusted to 6.5；Then reaction mixture is all transferred to 40mL high-pressure hydrothermal reaction kettle In, after clean carbon cloth is dipped vertically into solution, seal reaction kettle；Then reaction kettle is moved in electric furnace, and with 5 DEG C/min Speed be heated to 180 DEG C and react 9 hours.
After naturally cooling to room temperature, reaction kettle is opened, carbon cloth is taken out and alternately rinses each 3 with deionized water and alcohol It is secondary, then dry at 60 DEG C to get the NiS-MoS loaded to the carbon cloth2Heterogeneous nano-chip arrays structure.At room temperature, It is saved backup in drying box.
That loaded on carbon cloth is the NiS-MoS of high-purity2Composite material (see Fig. 1), this material do not change carbon The structure and pattern (see Fig. 2) of cloth are a large amount of criss-cross NiS-MoS at array-like in carbon cloth surfaces2Heterogeneous nanometer sheet (see Fig. 3).Wherein the diameter of carbon fiber is about 10 μm, the thickness of heterogeneous nanometer sheet about 30nm, diameter about 500nm；MoS2Uniformly It is coated on the surface of NiS (see Fig. 2-4).
The NiS-MoS of carbon cloth load obtained2Heterogeneous nano-chip arrays structure have excellent electrochemical catalysis hydrogen manufacturing, Oxygen performance processed.In 1molL-1KOH electrolyte in, reach 10mAcm-2When current density, hydrogen manufacturing overpotential is 106mV, Tafel slope is 56.7；Oxygen overpotential processed is 203mV, and Tafel slope is 77.4mVdec-1；In complete solution water, reach 10mA·cm-2Current density, it is only necessary to voltage 1.54V, and stabilizability decomposes water at least for 24 hours.

Claims (5)

1. the NiS-MoS of carbon cloth load2Heterogeneous nano-chip arrays structure, which is characterized in that the product is by three-dimensional carbon fiber The NiS-MoS of the array-like of cloth and its surface uniform load2Heterogeneous nanometer sheet is constituted；Be built in the product it is a kind of multistage Three-dimensional box rack and panel construction, using carbon fiber as conducting matrix grain, in the NiS-MoS of its surface uniform load array-like2Heterogeneous nanometer Piece, wherein MoS2It is uniformly wrapped on the surface NiS.
2. the NiS-MoS of carbon cloth load described in accordance with the claim 12The preparation method of heterogeneous nano-chip arrays structure, feature It is, using nickel acetate, ammonium molybdate, thiocarbamide as nickel source, molybdenum source and sulphur source, lauryl sodium sulfate is surfactant, is passed through One step hydro thermal method, directly carbon cloth surfaces uniformly, closely grow NiS-MoS2Heterogeneous nano-chip arrays structure；Successively include Following steps:
(1) that carbon cloth with acetone, 1-2mol/L aqueous hydrochloric acid solution and deionized water is successively cleaned by ultrasonic 0.5-1 respectively in advance is small When, and dried at 60 DEG C, it saves backup；
(2) it by the pure nickel acetate of commercially available analysis, ammonium molybdate, thiocarbamide and lauryl sodium sulfate powder investment beaker, adds Ionized water, which is sufficiently stirred, mixes it uniformly, and controlling acetic acid nickel concentration in mixed solution is 0.03-0.05mol/L, ammonium molybdate Concentration is 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, and lauryl sodium sulfate concentration is 0.15- 0.25mol/L；Recycle the pH value of the sodium hydrate aqueous solution adjusting reactant mixed solution of 0.5-1.0mol/L to 5.8-7.0 Between；
(3) after the reactant mixed solution for filling 50%-80% in a high pressure reaction kettle, it is dipped vertically into clean carbon cloth, is sealed Reaction kettle；
(4) reaction kettle is moved in electric furnace, and the rate of 5-20 DEG C/min is heated to 160-200 DEG C and keeps the temperature 8-12 hours；So After naturally cool to room temperature；
(5) after opening reaction kettle, carbon cloth is taken out from reaction kettle, and alternately rinsed 3-5 times with deionized water and alcohol；Then exist It is dried at 60 DEG C；
(6) at room temperature, it is saved backup in drying box.
3. preparation method according to claim 2, which is characterized in that in the step (1), carbon cloth is in advance respectively with third Ketone, 1-2mol/L aqueous hydrochloric acid solution and deionized water are successively cleaned by ultrasonic 0.5-1 hours, and dry at 60 DEG C.
4. preparation method according to claim 2, which is characterized in that in the step (2), nickel acetate, ammonium molybdate, thiocarbamide It is the commercially available pure powder reagent of analysis with lauryl sodium sulfate；Controlling acetic acid nickel concentration in reactant mixed solution is 0.03- 0.05mol/L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, dodecyl Sodium sulfate concentration is 0.15-0.25mol/L；Adjusting sodium hydrate aqueous solution concentration used in reactant mixed solution pH value is 0.5- 1.0mol/L, reactant mixed solution pH value is 5.8-7.0 after adjusting；The step (3) fills 50%- in a high pressure reaction kettle 80% reactant mixed solution, and carbon cloth is dipped vertically into wherein.
5. preparation method according to claim 2, which is characterized in that in the step (4), react heating schedule are as follows: with The rate of 5-20 DEG C/min is heated to 160-200 DEG C and keeps the temperature 8-12 hours, then naturally cools to room temperature.
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